Morphology-Reserved Synthesis of Discrete Nanosheets of CuO@SAPO-34 and Pore Mouth Catalysis for One-Pot Oxidation of Cyclohexane

Discrete nanosheets of silicon-doped AlPO₄ molecular sieves (SAPO-34) with a thickness of ≈7 nm have been prepared through morphology-reserved synthesis with a lamellar aluminum phosphate as precursor. Cages of the nanosheets are in situ incorporated with copper oxide clusters. The CuO@SAPO-34 nanosheets exhibit a large external surface area with a high number of (010) channel pores on the surface. Due to the thin morphology, copper oxide clusters occupy the outmost cages with a probability >50 %. The distinctive configuration facilitates a new concept of pore mouth catalysis, i.e., reactant molecules larger than the pores cannot enter the interior of the molecular sieves but can interact with the CuO clusters at “the mouth” of the pore. In heterogeneous catalysis, CuO@SAPO-34 nanosheets have shown top performance in one-pot oxidation of cyclohexane to adipic acid by O₂, a key compound for the manufacture of nylon-66, which is so far produced using non-green nitric acid oxidation.     

Catalytic CO Oxidation by O2 Mediated by Noble‐Metal‐Free Cluster Anions Cu2VO3–5−

Catalytic CO oxidation by molecular O₂ is an important model reaction in both the condensed phase and gas‐phase studies. Available gas‐phase studies indicate that noble metal is indispensable in catalytic CO oxidation by O₂ under thermal collision conditions. Herein, we identified the first example of noble‐metal‐free heteronuclear oxide cluster catalysts, the copper–vanadium bimetallic oxide clusters Cu₂VO_3–5^? for CO oxidation by O₂. The reactions were characterized by mass spectrometry, photoelectron spectroscopy, and density functional calculations. The dynamic nature of the Cu?Cu unit in terms of the electron storage and release is the driving force to promote CO oxidation and O₂ activation during the catalysis.     

Noble‐Metal‐Free Single‐Atom Catalysts CuAl4O7–9− for CO Oxidation by O2

The single copper atom doped clusters CuAl₄O_7–9^? can catalyze CO oxidation by O₂. The CuAl₄O_7–9^? clusters are the first group of experimentally identified noble‐metal free single atom catalysts for such a prototypical reaction. The reactions were characterized by mass spectrometry and density functional theory calculations. The CuAl₄O₉CO^? is much more reactive than CuAl₄O₉^? in the reaction with CO to generate CO₂. One adsorbed CO is crucial to stabilize Cu of CuAl₄O₉^? around +I oxidation state and promote the oxidation of another CO. The widely emphasized correlation between the catalytic reactivity of CO oxidation and Cu oxidation state can be understood at the strictly molecular level. The remarkable difference between Cu catalysis and noble‐metal catalysis was discussed.     

Fabrication of SAPO‐34 with Tuned Mesopore Structure

Crystalline SAPO‐34 molecular sieves with hierarchical network were synthesized employing polyethylene glycol (PEG) as the meso‐generating agent via a self‐assembly strategy. XRD, FESEM, N₂ adsorption‐desorption and FT‐IR spectroscopic analyses showed that PEG co‐template has a decisive role in tailoring the pore structure and producing a tuned structure from microporous towards the mesoporous structure. Also, addition of PEG favored the formation of more uniform and smaller crystals than the conventional SAPO‐34. In fact, PEG did not only control the size of crystals due to its crystal growth inhibiting (CGI) effect but also modified the morphology of the crystals and improved CSD (crystal size distribution) along with induction of mesopores into the porous structure. The modified SAPO‐34 would be recommended for selective formation of light olefins through the acid‐catalyzed reactions, such as the conversion of methanol to olefins/propylene (MTO/MTP) and propane dehydrogenation (PDH) to produce olefins with higher selectivity and catalyst stability than the conventional SAPO‐34.     

Electrochemical‐Reduction‐Assisted Assembly of a Polyoxometalate/Graphene Nanocomposite and Its Enhanced Lithium‐Storage Performance

Herein, we present an electrochemically assisted method for the reduction of graphene oxide (GO) and the assembly of polyoxometalate clusters on the reduced GO (rGO) nanosheets for the preparation of nanocomposites. In this method, the Keggin‐type H₄SiW₁₂O₄₀ (SiW₁₂) is used as an electrocatalyst. During the reduction process, SiW₁₂ transfers the electrons from the electrode to GO, leading to a deep reduction of GO in which the content of oxygen‐containing groups is decreased to around 5 %. Meanwhile, the strong adsorption effect between the SiW₁₂ clusters and rGO nanosheets induces the spontaneous assembly of SiW₁₂ on rGO in a uniformly dispersed state, forming a porous, powder‐type nanocomposite. More importantly, the nanocomposite shows an enhanced capacity of 275 mAh g^?1 as a cathode active material for lithium storage, which is 1.7 times that of the pure SiW₁₂. This enhancement is attributed to the synergistic effect of the conductive rGO support and the well‐dispersed state of the SiW₁₂ clusters, which facilitate the electron transfer and lithium‐ion diffusion, respectively. Considering the facile, mild, and environmentally benign features of this method, it is reasonable as a general route for the incorporation of more types of functional polyoxometalates onto graphene matrices; this may allow the creation of nanocomposites for versatile applications, for example, in the fields of catalysis, electronics, and energy storage.     

A Bio‐inspired Cu4O4 Cubane: Effective Molecular Catalysts for Electrocatalytic Water Oxidation in Aqueous Solution

Inspired by the cubic Mn₄CaO₅ cluster of natural oxygen‐evolving complex in Photosystem II, tetrametallic molecular water oxidation catalysts, especially M₄O₄ cubane‐like clusters (M=transition metals), have aroused great interest in developing highly active and robust catalysts for water oxidation. Among these M₄O₄ clusters, however, copper‐based molecular catalysts are poorly understood. Now, bio‐inspired Cu₄O₄ cubanes are presented as effective molecular catalysts for electrocatalytic water oxidation in aqueous solution (pH 12). The exceptional catalytic activity is manifested with a turnover frequency (TOF) of 267 s^?1 for [(L_Gly‐Cu)₄] at 1.70 V and 105 s^?1 for [(L_Glu‐Cu)₄] at 1.56 V. Electrochemical and spectroscopic study revealed a successive two‐electron transfer process in the Cu₄O₄ cubanes to form high‐valent Cu^III and Cu^IIIO^. intermediates during the catalysis.     

Nickel‐substituted cobalt ferrite nanoparticles supported on arginine‐modified graphene oxide nanosheets: Synthesis and catalytic activity

The amino acid arginine was used to modify the surface of graphene oxide nanosheets and then nickel‐substituted cobalt ferrite nanoparticles were supported on those arginine‐grafted graphene oxide nanosheets (Ni_0.5Co_0.5Fe₂O₄@Arg–GO). The prepared Ni_0.5Co_0.5Fe₂O₄@Arg–GO was characterized using flame atomic absorption spectroscopy, inductively coupled plasma optical emission spectrometry, energy‐dispersive spectroscopy, Fourier transform infrared spectroscopy, ultraviolet–visible spectroscopy, Raman spectroscopy, X‐ray diffraction, thermogravimetric analysis, scanning electron microscopy and transmission electron microscopy. The application of Ni_0.5Co_0.5Fe₂O₄@Arg–GO as a catalyst was examined in a one‐pot tandem oxidative cyclization of primary alcohols with o ‐phenylenediamine to benzimidazoles under aerobic oxidation conditions. The results showed that 2‐phenylbenzimidazole derivatives were successfully achieved using Ni_0.5Co_0.5Fe₂O₄@Arg–GO nanocomposite catalyst via the one‐pot tandem oxidative cyclization strategy.     

Cu‐Based Nanoparticles as Emerging Environmental Catalysts

This account provides an overview of current research activities on nanoparticles containing the earth‐abundant and inexpensive element copper (Cu) and Cu‐based nanoparticles, especially in the field of environmental catalysis. The different synthetic strategies with possible modification of the chemical/ physical properties of these nanoparticles using such strategies and/or conditions to improve catalytic activity are presented. The design and development of support and/or bimetallic systems (e. g., alloys, intermetallic, etc.) are also included. Herein, we report synthetic approaches of Cu and Cu‐based nanoparticles (monometallic copper, bimetallic copper and copper (II) oxide nanoparticles/nanostructures) and impregnation of such nanoparticles onto support material (e. g., Co₃O₄ nanostructure), along with their applications as environmental catalyst for various oxidation and reduction reactions. Finally, this account provides necessary advances and perspectives of Cu‐based nanoparticles in the environmental catalysis.     

NH3‐Driven Benzene C−H Activation with O2 that Opens a New Way for Selective Phenol Synthesis

Catalytic benzene C?H activation toward selective phenol synthesis with O₂ remains a stimulating challenge to be tackled. Phenol is currently produced industrially by the three‐steps cumene process in liquid phase, which is energy‐intensive and not environmentally friendly. Hence, there is a strong demand for an alternative gas‐phase single‐path reaction process. This account documents the pivotal confined single metal ion site platform with a sufficiently large coordination sphere in β zeolite pores, which promotes the unprecedented catalysis for the selective benzene hydroxylation with O₂ under coexisting NH₃ by the new inter‐ligand concerted mechanism. Among alkali and alkaline‐earth metal ions and transition and precious metal ions, single Cs⁺ and Rb⁺ sites with ion diameters >0.300 nm in the β pores exhibited good performances for the direct phenol synthesis in a gas‐phase single‐path reaction process. The single Cs⁺ and Rb⁺ sites that possess neither significant Lewis acidic?basic property nor redox property, cannot activate benzene, O₂, and NH₃, respectively, whereas when they coadsorbed together, the reaction of the inter‐coadsorbates on the single alkali‐metal ion site proceeds concertedly (the inter‐ligand concerted mechanism), bringing about the benzene C?H activation toward phenol synthesis. The NH₃‐driven benzene C?H activation with O₂ was compared to the switchover of the reaction pathways from the deep oxidation to selective oxidation of benzene by coexisting NH₃ on Pt₆ metallic cluster/β and Ni₄O₄ oxide cluster/β. The NH₃‐driven selective oxidation mechanism observed with the Cs⁺/β and Rb⁺/β differs from the traditional redox catalysis (Mars‐van Krevelen) mechanism, simple Langmuir‐Hinshelwood mechanism, and acid?base catalysis mechanism involving clearly defined interaction modes. The present catalysis concept opens a new way for catalytic selective oxidation processes involving direct phenol synthesis.     

A Stable Extra‐Large‐Pore Zeolite with Intersecting 14‐ and 10‐Membered‐Ring Channels

The development of inorganic frameworks with extra‐large pores (larger than 12‐membered rings) has attracted considerable attention because of their potential applications in catalysis, the separation of large molecules, and so forth. We herein report the synthesis of the new extra‐large‐pore zeolite NUD‐2 by using the supramolecular self‐assembly of simple aromatic organic cations as structure‐directing agents (SDAs). NUD‐2 is a high‐silicon‐content germanosilicate with interconnecting 14×10‐membered‐ring channels. The SDAs in NUD‐2 can be removed by calcination in air at 550 °C to yield permanent pores with a BET surface area of 500 m²g^?1. Both germanium and organic cations in NUD‐2 can also be removed by treatment with acid at lower temperature, thus not only affording recycling of germanium and SDAs, but also providing a highly stable siliceous zeolite. In addition, aluminum ions can be incorporated into the framework of NUD‐2. The NUD‐2 structure is yet another extra‐large‐pore zeolite synthesized by using the supramolecular self‐assembling templating approach, thus demonstrating that this approach is a general and applicable strategy for synthesis of new large‐ and extra‐large‐pore zeolites.     

Enrichment,incorporation and oxidation of copper during anodising of aluminium–copper alloys

Porous anodic oxides generated on copper‐containing aluminium alloys are less regular than anodic oxides generated on pure aluminium. Specifically, a porous oxide morphology comprising layers of embryo pores, generated by a cyclic process of oxide film growth and oxygen evolution, is generally observed. In this work, the relation between the oxidation behaviour of copper during anodising and the specific porous oxide film morphology was investigated by electrochemical techniques, transmission electron microscopy and Rutherford backscattering spectroscopy (RBS). It was found that the anodising potential determines the oxidation behaviour of copper, and the latter determines the porous oxide morphology. At low voltage, relatively straight pores with continuous cell walls were obtained on Al? Cu alloys, but selective oxidation of aluminium atoms resulted in the occlusion of copper‐containing metallic nanoparticles in the anodic film. At higher potentials, copper oxidation promoted oxygen evolution within the barrier layer, and generation of a less regular film morphology. RBS, performed on Al? Cu alloy specimens, revealed a high volume fraction of copper atoms in the anodic films generated at low potentials and a reduced amount of copper atoms in the anodic oxide films generated at high potentials. Copyright © 2009 John Wiley & Sons, Ltd.     

Visible‐Light‐Driven Water Oxidation with a Polyoxometalate‐Complexed Hematite Core of 275 Iron Atoms

Although metal oxide nanocrystals are often highly active, rapid aggregation (particularly in water) generally precludes detailed solution‐state investigations of their catalytic reactions. This is equally true for visible‐light‐driven water oxidation with hematite α‐Fe₂O₃ nanocrystals, which bridge a conceptual divide between molecular complexes of iron and solid‐state hematite photoanodes. We herein report that the aqueous solubility and remarkable stability of polyoxometalate (POM)‐complexed hematite cores with 275 iron atoms enable investigations of visible‐light‐driven water oxidation at this frontier using the versatile toolbox of solution‐state methods typically reserved for molecular catalysis. The use of these methods revealed a unique mechanism, understood as a general consequence of fundamental differences between reactions of solid‐state metal oxides and freely diffusing “fragments” of the same material.     

Thin Films that Consist of CuO Mesocrystal Nanosheets: An Application of Microbial‐Mineralization‐Inspired Approaches to Thin‐Film Formation

Thin films of copper oxides can be synthesized on substrates by using approaches that are inspired by microbial mineralization processes. In nature, precipitates of manganese and iron oxides with controlled oxidation states and crystal phases are produced through biomineralization by microorganisms. We have previously reported microbial‐mineralization‐inspired approaches that are comprised of direct and intermediate routes for the controlled syntheses of transition‐metal oxides. Herein, these approaches are applied to the thin‐film formation and coating of copper oxides and a related compound with controlled crystal phases and morphologies. Thin films of CuO, Cu₂O, and Cu₂(OH)₃Cl were selectively synthesized by using direct or intermediate routes. Notably, CuO mesocrystal nanosheets formed a thin film over the whole of the substrate. The resultant CuO mesocrystal nanosheets showed enhanced properties for the electrochemical detection of dopamine. This study shows the potential applicability of microbial‐mineralization‐inspired approaches to thin‐film coatings.     

The Effect of pH Values on the Synthesis,Microstructure and Photocatalytic Activity of Ce‐Bi2O3 by a Two‐Step Hydrothermal Method

In this study, the effect of pH values on the microstructure and photocatalytic activity of Ce‐Bi₂O₃ under visible light irradiation was investigated in detail. In alkaline condition (e.g. pH = 9), the as‐prepared Ce‐Bi₂O₃ exhibited an agglomerated status and mesoporous structures without a long‐range order. While in weak acid condition (e.g. pH = 5), the Ce‐Bi₂O₃ exhibited a best morphology with irregular nanosheets. Correspondingly, it possessed largest surface area (24.641 m² g^?1) and pore volume (9.825E‐02 cm³ g^?1). These unique nanosheets can offer an attachment for pollutant molecules and reduce the distance of electron immigration from inner to surface, thus facilitating the separation of photoelectron and hole pairs. Compared with the pure Bi₂O₃, the band gap of Ce‐Bi₂O₃ prepared at different pH was much lower. Among them, the band gap of Ce‐Bi₂O₃ (pH of 5) was lowest (2.61 eV). Ce‐Bi₂O₃ (pH of 5) exhibited as tetragonal crystal with the bismuth oxide in the form of the composites, which could reduce the band gap width or suppress the charge‐carrier recombination, subsequently possessing great photocatalytic activity for acid orange II under visible light irradiation. After 2 h degradation under visible light, the degradation rate of acid Orange II was up to 96.44% by Ce‐Bi₂O₃ prepared at pH 5. Overall, it can be concluded that the pH values had effects on the microstructure and photocatalytic activity of Ce‐Bi₂O₃ catalysts.     

Surfactant‐Free Nonaqueous Synthesis of Plasmonic Molybdenum Oxide Nanosheets with Enhanced Catalytic Activity for Hydrogen Generation from Ammonia Borane under Visible Light

Plasmonic materials have drawn emerging interest, especially in nontraditional semiconductor nanostructures with earth‐abundant elements and low resistive loss. However, the actualization of highly efficient catalysis in plasmonic semiconductor nanostructures is still a challenge, owing to the presence of surface‐capping agents in their synthetic procedures. To fulfill this, a facile non‐aqueous procedure was employed to prepare well‐defined molybdenum oxide nanosheets in the absence of surfactants. The obtained MoO_3‐x nanosheets display intense absorption in a wide range attributed to the localized surface plasmon resonances, which can be tuned from the visible to the near‐infrared region. Herein, we demonstrate that such plasmonic semiconductor nanostructures could be used as highly efficient catalysts that dramatically enhance the hydrogen‐generation activity of ammonia borane under visible light irradiation.     

CO2‐Assisted Fabrication of Two‐Dimensional Amorphous Molybdenum Oxide Nanosheets for Enhanced Plasmon Resonances

As a remarkable class of plasmonic materials, two dimensional (2D) semiconductor compounds have attracted attention owing to their controlled manipulation of plasmon resonances in the visible light spectrum, which outperforms conventional noble metals. However, tuning of plasmonic resonances for 2D semiconductors remains challenging. Herein, we design a novel method to obtain amorphous molybdenum oxide (MoO₃) nanosheets, in which it combines the oxidation of MoS₂ and subsequent supercritical CO₂‐treatment, which is a crucial step for the achievement of amorphous structure of MoO₃. Upon illumination, hydrogen‐doped MoO₃ exhibits tuned surface plasmon resonances in the visible and near‐IR regions. Moreover, a unique behavior of the amorphous MoO₃ nanosheets has been found in an optical biosensing system; there is an optimum plasmon resonance after incubation with different BSA concentrations, suggesting a tunable plasmonic device in the near future.     

CuII‐Catalyzed Oxidative Formation of 5‐Alkynyltriazoles

In an alcoholic solvent under the catalysis of Cu(OAc)₂?H₂O, organic azide and terminal alkyne could oxidatively couple to afford 5‐alkynyl‐1,2,3‐triazole (alkynyltriazole) at room temperature under an atmosphere of O₂ in a few hours. The involvement of 1,5‐diazabicyclo[4.3.0]non‐5‐ene (DBN) is essential, without which the redox neutral coupling instead proceeds to produce 5‐H‐1,2,3‐triazole (protiotriazole) as the major product. Therefore, DBN switches the redox neutral coupling between terminal alkyne and organic azide, the copper‐catalyzed “click” reaction to afford protiotriazole, to an oxidation reaction that results in alkynyltriazole. The organic base DBN is effective in accelerating the copper(II)‐catalyzed oxidation of terminal alkyne or copper(I) acetylide, which is intercepted by an organic azide to produce alkynyltriazole. The proposed mechanistic model suggests that the selectivity between alkynyl‐ and protiotriazole, and other acetylide or triazolide oxidation products is determined by the competition between copper(I)‐catalyzed redox neutral cycloaddition and copper(II)/O₂‐mediated acetylide oxidation after the formation of copper(I) acetylide.     

Self‐Assembling of Er2O3–TiO2 Mixed Oxide Nanoplatelets by a Template‐Free Solvothermal Route

An easy solvothermal route has been developed to synthesize the first mesoporous Er₂O₃–TiO₂ mixed oxide spherical particles composed of crystalline nanoplatelets, with high surface area and narrow pore size distribution. This synthetic strategy allows the preparation of materials at low temperature with interesting textural properties without the use of surfactants, as well as the control of particle size and shape. TEM and Raman analysis confirm the formation of nanocrystalline Er₂O₃–TiO₂ mixed oxide. Mesoscopic ordered porosity is reached through the thermal decomposition of organic moieties during the synthetic process, thus leading to a template‐free methodology that can be extended to other nanostructured materials. High specific surface areas (up to 313 m² g^?1) and narrow pore size distributions are achieved in comparison to the micrometric material synthesized by the traditional sol–gel route. This study opens new perspectives in the development, by solvothermal methodologies, of multifunctional materials for advanced applications by improving the classical pyrochlore properties (magnetization, heat capacity, catalysis, conductivity, etc.). In particular, since catalytic reactions take place on the surface of catalysts, the high surface area of these materials makes them promising candidates for catalysts. Furthermore, their spherical morphology makes them appropriate for advanced technologies in, for instance, ceramic inkjet printers.     

Organic‐Free Synthesis of Silicoaluminophosphate Molecular Sieves

Silicoaluminophosphate (SAPO) molecular sieves are an important class of microporous materials and are useful for industrial catalysis and separations. They have been synthesized exclusively by the use of expensive and environmentally unfriendly organic structure‐directing agents. Now the synthesis of SAPO molecular sieves is reported with MER, EDI, GIS, and ANA topologies under wholly inorganic conditions. Multinuclear MAS NMR analyses demonstrate the presence of Si, Al, and P atoms in their frameworks. These SAPO materials all have unusually high framework charge densities (0.25–0.46), owing to the small size of alkali metal cations used as an inorganic structure‐directing agent. A continuous Si increase in the synthesis gel for MER‐type SAPO molecular sieves led to the formation of framework Si(0Al) units, decreasing the number of extra‐framework cations per unit cell and thus making the resulting solid useful for CO₂ adsorption.     

Graphene oxide‐catalyzed CSp3–H activation of methylarenes in aqueous medium: A unified metal‐free access to amides and benzimidazoles

Graphene oxide (GO)‐catalyzed selective synthesis of amides via C_Sp3–H activation of methylarenes and consequent C–N bond formation with anilines under aqueous medium has been described. Oxygen functionality allied with GO surface played a dual role both as acid catalyst and oxidizing agent to some extent. However, GO has a copious effect on the reaction, shown by a high TOF value with TBHP as co‐oxidant. The decisive role of carboxylic acid functional groups on GO nanosheets in this metal‐free strategy has been confirmed and was monitored by various analytic techniques viz. Fourier transform‐infrared, UV–Vis, Raman and XPS. A plausible mechanism was proposed by control experiments and by the isolation of the intermediate. Over‐oxidation of methylarenes was not detected, and high recyclability of the carbocatalyst with its heterogeneous behavior facilitated the isolation and purification of the desired products. We have further explored the utility of this process for the chemoselective synthesis of benzimidazoles.